1. Field of the Invention
This invention relates to compositions and processes for non-permanently coloring keratinous fibers, particularly human hair, comprising the use of sulfo-containing, water-dispersible, colored polymers wherein the colorant moiety is incorporated into or onto a carbonyloxy and/or carbonylamide backbone of the polymer. The compositions preferably additionally comprise nonionic hydrophobically modified associative thickeners. The colored polymers are uniquely designed to offer cosmetically desirable color coatings on hair and to be easily dispersible in hot water, yet offer excellent resistance to redispersion in water at room temperature, which prevents color bleeding if the hair becomes wet while colored with the polymers. It may be further desirable to thicken these dispersions in order to prevent dripping or running of the dispersion during application. In addition, in some applications, thick lotions and gels can be advantageously used to apply colored polymer dispersions to hair. We have found that nonionic, hydrophobically modified associative thickeners can be conveniently used to increase product viscosity without significantly compromising the performance of the colored polymers.
2. Description of the Prior Art
It is very desirable to offer users of hair colorants the option of coloring their hair in such a manner that the effect of the coloring treatment can be easily removed or reversed by the use of regular, commercial shampoo products. Uncertainty and concern about selecting the right color, the wish to easily experiment with different hair tonalities, and the changing requirements of fashion and lifestyles, all contribute to the desirability of non-permanent hair coloring products. Additionally, there is a frequent need to modulate or adjust the color produced by prior, more permanent color treatments. This is especially desirable in order to compensate for the gradual color fading which is always observed after using even the most permanent hair coloring products.
Another application for hair coloring materials which can easily and reversibly color hair comprises incorporating them into frequently used hair care products such as conditioners, mousses and setting lotions. This allows the user to conveniently tone or introduce color highlights in the hair without the need for a separate coloring process.
Customarily, hair is colored using low molecular weight compounds which penetrate the keratinous fibers. This approach has been successful for producing permanent and semipermanent color effects on hair. It requires, however, some affinity between the chromophore-bearing molecules of the colorant and the fibers and, as a result, it becomes very difficult even after repeated shampooing to remove all the colorant which has penetrated into the hair. In addition, these permanent and semi-permanent treatments are very sensitive to variations in the quality of hair among different individuals. Treatments which do not penetrate the hair fibers, but which color hair by depositing colored materials only on the hair fiber surface, are practically insensitive to such variations, can be easily removed and have therefore been proposed and used for the non-permanent, i.e. totally reversible, coloring of hair.
U.S. Pat. No. 4,559,057 describes the use of insoluble pigments. Due to their poor adherence to the hair surface, they are to be used together with a polymeric binder in order to reduce rub-off of the color and produce acceptable color coatings on hair. Insoluble pigments are very different from the soluble dyes of the present invention.
U.S. Pat. No. 4,804,719 discloses polymeric compositions which contain carbonyloxy and carbonylamide links, particularly polyesters and polyesteramides, having water solubilizing sulfonate groups and colorants, copolymerized onto or into the polymer backbone. It is indicated in this patent that these polymers are useful in adhesives, coating materials, films and packaging materials. It is also stated therein that aqueous dispersions of these materials have utility as inks, paints and other industrial coatings, all of which are intended to be permanent in nature. No disclosure is made relating to the specific art of dyeing keratinous fibers, non-permanently or otherwise.
Various examples of thermally stable industrial colorants useful for manufacturing colored polymers through incorporation into or onto the sulfopolyester polymer are described in U.S. Pat. Nos. 2,571,319; 3,034,920; 3,104,233; 3,372,138; 3,417,048; 3,489,713; 3,278,486; 3,359,230; 3,401,192; 3,417,048; 3,424,708; 4,049,376; 4,080,355; 4,088,650; 4,116,923; 4,141,881; 4,202,814; 4,231,918; 4,267,306; 4,279,802; 4,292,232; 4,344,767; 4,359,570; 4,403,092; 4,477,635; 4,594,400; 4,617,373; 4,617,374; 4,740,581; 4,745,173; 4,808,677; 4,892,922; 4,892,923; 4,958,043; 4,999,418; 5,030,708; 5,032,670; 5,075,491; 5,086,161; 5,102,980; 5,106,942; 5,151,516; 5,179,207; 5,194,571; 5,274,072; 5,281,658 and 5,384,377. None of the above references suggest the application of the industrial colorants to human hair.
U.S. Pat. Nos. 4,300,580 and 5,158,762 disclose hair spray compositions comprising colorless, sulfo-containing, water dispersible polyesters which are useful for giving hair a firm texture and for holding hair in a desired arrangement for a certain length of time. These polymers are fundamentally different from those in the present invention in that the reference does not teach or suggest colored molecules. Inherently, they also fail to suggest incorporating colored molecules into or onto the polymeric backbone.
In order for colored polymers to be useful in non-permanent hair coloring they must fulfill a number of requirements which are quite distinct from those necessary for hair spray resins. Specifically, they must form films that strongly adhere to the hair surface. Such films must also remain flexible enough under different temperature and relative humidity conditions so as to withstand the bending of hair without fracturing and separating from the fibers. They should, however, be hard enough to prevent the transfer of color if rubbed against parts of the body, clothing, etc. They must be easily and completely removable by shampooing and yet, in order to prevent color bleed, they cannot be easily redispersed or resolubilized by contact with water at room temperature. They must also obviously be safe and not irritate or stain the skin. In contrast, hair spray and other hair styling colorless polymers are practically invisible to the naked eye. As a result, rub-off onto other surfaces, moderate flaking of fractured film particles, incomplete shampoo removability, and "bleed" upon exposure to water would not be noticed.
Unlike the aforementioned colorless polymers, the intense coloration of the polymers described in this invention would make even small-trace quantities of them quite obvious, and easily noticeable on hair, other surfaces and in solution. It can thus be easily understood that the requirements for hair spray or hair styling colorless polymers are intrinsically far less stringent than those for colored polymers for use in non-permanent hair coloring products. It is then by no means anticipated that, if a certain type of colorless polymer useful in hair fixatives could be made colored even without changing its properties, it would then also be advantageously useful for non-permanent hair coloring. It is moreover well known to those familiar with polymer chemistry and properties that it is extremely difficult to incorporate a new and different comonomer into or onto a polymer backbone without substantially changing the properties of the polymer.
U.S. Pat. No. 3,251,743 to BASF and U.S. Pat. Nos. 3,535,255; 3,567,678; 3,597,468; 3,617,165; 3,619,101; 3,720,653; 3,763,086; 3,797,994 and 3,915,635 to L'Oreal disclose colored polymers and compositions for coloring hair. These polymers are structurally different from those disclosed in the present invention in that they do not have solubilizing sulfonate groups and they have a hydrocarbon backbone. They rely instead on carboxy groups which in some cases have to be neutralized by organic or inorganic bases in order to make these polymers water soluble. Alternatively, they can be dissolved in alcohol or alcohol-water solutions.
U.S. Pat. No. 4,182,612 describes a new class of water soluble cationic colored polymers useful for dyeing hair prepared by the colorant reaction of chromophores with selected polymer backbones. U.S. Pat. No. 4,228,259 also describes the preparation and use for dyeing hair of water soluble cationic colored polymer having various amine groups wherein said amine groups are either a part of or aid in the linking to the polymer chain of an aryl or arylaliphatic chromophore. The polymers in both of these patents are different from those in the present invention in that they do not have water solubilizing sulfonate groups and the structure of the backbone is very different. In addition, and by design, their cationic nature gives them a very strong affinity for hair, making them very shampoo resistant and therefore not suitable for temporary, i.e. easily removable, hair coloring treatments.
U.S. Pat. Nos. 4,051,138; 4,144,252; and 4,169,203 to Dynapol describe the composition of water soluble colored anionic polymers. These polymers are different from those of the present invention in various important respects. The polymer backbone is a simple hydrocarbon chain whereas the polymers described in this invention contain carbonyloxy and/or carbonylamide moieties in the backbone. Although the polymers in these three patents similarly have water solubilizing sulfonate groups, these polymers were mainly designed to be used as water soluble colorants in foods and beverages and are so readily and quickly water soluble that they would show excessive color bleeding if used to color hair. In addition, they are not good film forming polymers and, because of these characteristics, they are not useful as substantive hair colorants. In contrast, since the sulfo-containing polymers of the present invention are not readily water-soluble, less bleeding is observed. Thus, they are a major improvement over the Dynapol compounds.
In summary, the colored polymers used in this invention have chemical structures different from the colored polymers proposed as hair colorants in the prior art. The combination of the water-solubilizing sulfonate groups, colored monomers, and the structure of the polymer backbone, which may include three to four additional monomers, is unique. Unexpectedly, this type of structure produces colored polymers which are highly resistant to dispersion in ambient temperature water. As a result, when these polymers are present on the hair surface as dry films, color bleed upon exposure to ambient temperature water is insignificant.
It is well known that the viscosity of hair cosmetic products is usually adjusted in order to facilitate performance and ease of application. When such products are designed for use on the scalp, their viscosity must be sufficiently low so that they can be easily and uniformly distributed throughout the relatively large mass of hair, but not so low that the product will drip or flow on the face, neck, etc. of the user. In other cases, as when treating various types of facial hair, higher viscosity may be desirable. These considerations are especially important for hair coloring products, as usually they must remain on the hair for a relatively long time in order for dyeing to take place. A wide variety of both natural and synthetic viscosity increasing agents (thickeners) are commercially available for use in hair products and in haircoloring products in particular.
U.S. Pat. No. 3,811,830 discloses compositions for the semipermanent dyeing of hair and mentions a series of thickeners which are suitable for this application. These include hydroxybutylcellulose, hydroxyethylcellulose, methyl cellulose, sodium carboxymethylcellulose, sodium alginate, and magnesium aluminum silicate. Semipermanent haircoloring compositions produce coloring effects which only survive a relatively small number of shampooings, and do not require the use of an oxidizing agent to develop the color. With permanent oxidative hair coloring compositions, the coloration imparted to the hair is relatively insensitive to repeated shampooing. Oxidative hair coloring products comprising intermediates and couplers usually involve the use of a two part system. The rheology of many such products is usually adjusted by the use of a low viscosity dye lotion which in addition to the intermediates and couplers contains a high level of surfactants and organic solvents, and which upon mixture with a highly aqueous solution of the oxidizing agent forms a dye mixture with the desired gel-like consistency. U.S. Pat. Nos. 3,388,627; 4,563,188; 5,503,640; 5,518,505; 5,500,021 disclosing oxidative hair dyeing compositions exemplify this approach. These patents also mention various thickeners including sodium alginate, gum arabic, cellulose derivatives, such as methylcellulose hydroxyethylcellulose, sodium carboxymethylcellulose, acrylic polymers, such as the sodium salt of polyacrylic acid, and inorganic thickeners, such as bentonite, which can be used to further adjust the viscosity of this type of product.
A third category of hair coloring products is based on temporary coloring of human hair. The coloring effects produced by these products can be easily removed by shampooing the hair once. Whereas both semipermanent and permanent hair coloring products are normally rinsed off the hair after the treatment is completed, temporary hair coloring products may be advantageously allowed to remain on the hair after application. When products are rinsed following application, thickeners do not have to perform beyond this stage. On the other hand, with no-rinse non-permanent hair coloring products, as is the case in the present invention, the thickener and all the other product ingredients are left on the hair surface after product application. In this instance, any of these ingredients may have an effect on the feel, appearance and behavior of the treated hair, as well as on the physical properties of colored deposit which is left on the fiber surface. As a result, the selection of product adducts for a leave-on product, can present unique technical difficulties. In the case of thickeners, the materials must not only perform well during application, but must also not negatively interfere with the overall after-treatment performance of the product.
U.S. Pat. Nos. 3,251,743; 3,535,255; 3,567,678; 3,597,468; 3,617,165; 3,619,101; 3,720,653; 3,763,086; 3,797,994; 3,915,635; and 4,182,612 referred to above, which disclose colored polymer compositions and methods for the temporary coloring of hair, mention that the compositions may contain additional colorless polymers to adjust the physical properties of the dyeing systems, and/or other additives conventionally used in such cosmetics, but do not make reference to any specific type of thickener which could advantageously be used in the practice of those inventions.
U.S. Pat. No. 4,228,259 which discloses "Water Soluble Cationic Polymer Dye Compounds and Process for Producing Same", mentions thickening agents which can be cellulosic derivatives such as carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethylcellulose.
Thickeners which differ from the ones referred to in the above patents are the hydrophobically modified associative thickeners. By "hydrophobically modified associative thickeners" is meant ionic or nonionic colorless, hydrophilic, water soluble polymers which have been modified by the incorporation of a sufficient amount of hydrophobic substituents either into their backbone or as side groups in order to make the polymers less water soluble allowing them to function as viscosity increasing agents. The degree of hydrophobic substitution is kept small in order not to render the modified polymer water insoluble. Aqueous solutions of these polymers have unusual rheological properties which are thought to arise from intermolecular associations of neighboring hydrophobic groups. These associations give rise to the formation of reversible three dimensional network structures. The regions of intermolecular hydrophobic association are also areas of high affinity for surfactant interactions. At low concentrations, surfactants interact mainly with the hydrophobic segments of the polymer, strengthening the network and producing an increase in the viscosity of the system. At higher concentrations, the hydrophobic segments of the polymer are solubilized within surfactant micelles, the network is destabilized and viscosity decreases. See: "Surfactant Interactions with HUER Associating Polymers" and references therein, Kewei Zhang, Bai Xu, Mitchell A. Winnik and Peter M. MacDonald, The Journal of Physical Chemistry, 1996, 100, pages 9834-9841!.
U.S. Pat. No. 4,155,892, ("Polyurethane Thickeners for Aqueous Compositions") assigned to Rohm and Haas Company, discloses aqueous systems which are thickened by incorporation of nonionic polyurethanes having at least three low molecular weight hydrophobic groups. The hydrophobic groups together contain a total of at least 20 carbon atoms and are linked through hydrophilic (water soluble) groups containing polyether segments of at least about 1500 molecular weight. The molecular weight of these polyurethanes is of the order of about 10,000 to 200,000.
Claimed in this patent are compositions comprising these polymers and "a cosmetically active material". Rohm and Haas trade literature on Aculyn.RTM. 44, an example of this type of compound, recommends the use of these materials in various cosmetic compositions including hair conditioners, aqueous antiperspirants, silicone emulsions, oxidizer containing hair dyes and cationic and sunscreen lotions.
U.S. Pat. No. 5,478,562, ("Cosmetic Composition Containing at Least One Surface-Active Agent of the Alkly Polyglycoside and/or Polyglycerolated Type and at Least One Polyurethane") assigned to L'Oreal, discloses cosmetic compositions containing the aforementioned surface agents and hydrophobically modified associative polyurethanes thickeners of the type disclosed in the Rohm and Haas patent. Compositions and processes for the washing and treatment of hair and skin are among the claims of the L'Oreal patent. The compositions of the present invention do not include surface active agents of the alkyl polyglycoside or polyglycerolated type.
A second type of hydrophobically modified associative thickener consists of certain nonionic modified cellulosic ethers. These materials which are disclosed in U.S. Pat. No. 4,228,277 assigned to Hercules Incorporated, have relatively low molecular weights but are capable of producing highly viscous aqueous solutions in practical concentrations. These materials have a sufficient degree of nonionic substitution selected from the groups consisting of methyl, hydroxyethyl and hydroxypropyl to cause them to be water soluble and are further substituted with a hydrocarbon radical having from about 10 to 24 atoms in amounts between about 0.2 weight percent and the amount which renders the cellulose ether less than 1% by weight soluble in water.
This patent teaches the use of these materials in shampoo formulations. Technical literature from the AQUALON Company teaches the use of these materials in hand and body lotions, shampoos and liquid soaps. U.S. Pat. No. 4,683,004, ("Foamable Compositions and Processes for Use Thereof") assigned to Union Carbide Corporation, discloses the use of the above materials in compositions for cosmetic applications to hair and skin which, in addition to the AQUALON thickeners, comprise one or more of a surfactant, a water-miscible alcohol, an oil emulsified in the water of the foamable composition, and a water soluble moisturizer. The compositions of the present invention do not comprise an emulsified oil or a water soluble moisturizer.
U.S. Pat. No. 5,100,657 (The Procter & Gamble Co.) claims hair conditioning compositions, the most relevant of which comprise: (a) hydrophobically modified cellulosic associative thickeners of the type disclosed in U.S. Pat. Nos. 4,228,277 (HMCAT-'277), a water insoluble surfactant, a compatible solvent, a silicone conditioning agent, and a fatty aclohol, and (b) (HMCAT-'277), hydrogenated tallow amide DEA, a chelating agent, water, a combination of a volatile silicone fluid and a silicone gum, dihydrogenated tallow dimethyl ammonium chloride, and a fatty alcohol. It also claims methods for providing conditioning to hair comprising treating the hair with the above compositions. The compositions of the present invention do not comprise most of the ingredients included in the compositions claimed in this patent.
U.S. Pat. No. 5,100,658 (The Procter & Gamble Co.) claims hair cosmetic compositions, the most relevant of which comprise: (a) a hydrophobically modified nonionic water soluble polymer which comprises a water soluble backbone and hydrophobic groups selected from the group consisting of C.sub.8 -C.sub.12 alkyl, aryl alkyl and alkyl aryl groups and mixtures thereof, wherein the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is from about 10:1 to about 1000:1, a water soluble polymeric thickener, a compatible solvent, and an active cosmetic component selected from the group consisting of conditioning agents, antidandruff aids, hair growth promoting aids, perfumes, dyes, pigments, sunscreens, hair holding polymers, and mixtures thereof; and (b) same as (a), but where the hydrophobically modified polymer is a HMCAT-'277. The compositions of the present invention do not comprise most of the ingredients included in the compositions claimed in this patent.
U.S. Pat. No. 5,104,646 (The Procter & Gamble Co.) claims hair cosmetic compositions, the most relevant of which comprise: (a) a hydrophobically modified nonionic water soluble polymer which comprises a water soluble backbone and hydrophobic groups selected from the group consisting of C.sub.8 -C.sub.2 alkyl, aryl alkyl and alkyl aryl groups and mixtures thereof, wherein the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is from about 10:1 to about 1000:1, a water insoluble surfactant, a compatible solvent, and an active cosmetic component selected from the group consisting of conditioning agents, antidandruff aids, hair growth promoting aids, perfumes, dyes, pigments, sunscreens, hair holding polymers, and mixtures thereof; (b) same as (a), but where the hydrophobically modified polymer is a HMCAT-'277; (c) a HMCAT-'277, a water insoluble surfactant, a chelating agent, a distributing aid selected from the group consisting of xanthan gum and dextran, a compatible solvent, and an active hair care component; (d) a HMCAT-'277, a water insoluble surfactant, a compatible solvent, and an active hair care component comprising a silicone conditioning agent and fatty alcohol; and (e) a
HMCAT-'277, hydrogenated tallow amide DEA, a chelating agent, an active hair care component, a silicone conditioning agent, dehydrogenated tallow dimethyl ammonium chloride and a fatty alcohol. The compositions of the present invention do not comprise most of the ingredients included in the compositions claimed in this patent.
U.S. Pat. No. 5,106,609 (The Procter & Gamble Co.) claims hair cosmetic compositions, the most relevant of which comprise: (a) a hydrophobically modified nonionic water soluble polymer which comprises a water soluble backbone and hydrophobic groups selected from the group consisting of C.sub.8 -C.sub.12 alkyl, aryl alkyl and alkyl aryl groups and mixtures thereof, wherein the ratio of the hydrophilic portion to the hydrophobic portion of the polymer is from about 10:1 to about 1000:1, a water insoluble surfactant, a compatible solvent, and an active cosmetic component; (b) same as (a), but where the hydrophobically modified polymer is a HMCAT-'277; (c), same as (b), but additionally comprising a water soluble polymer material having a molecular weight greater than about 20,000; (d) same as (b), but additionally comprising a chelating agent; (e) same as (c), but additionally comprising a chelating agent; (f) same as (b), were the said active cosmetic component comprises an active hair care component; (g) same as (e), wherein the active hair care component is selected from the group consisting of conditioning agents, antidandruff aids, hair growth promoters, perfumes, dyes, pigments, hair holding polymers, and mixtures thereof; (h) same as (f), wherein the haircare components are various types of silicone materials; and (i) other compositions comprising related combinations. The compositions of the present invention do not comprise most of the ingredients included in the compositions claimed in this patent.
A third type of hydrophobically modified associative thickener are the hydrophobically modified polyacrylates. A commercially available example is Aculyn 22.RTM. which is described in the Rohm and Haas Company trade literature as a hydrophobically modified associative acrylic polymeric thickener containing acid carboxyl (anionic) functional groups. The same literature recommends the use of Aculyn 22.RTM. in hair styling gels, foaming facial cleansers, specialty shampoos, curl activators, and depilatories. Carbopol.RTM. ETD 2020 from B. F. Goodrich is another example of a commercially available anionic hydrophobically modified polyacrylic acid thickener. U.S. Pat. No. 5,376,146 discloses a system for adjusting the viscosity of an oxidative dye system which relies on a pH change on mixing an alkaline dye lotion, with a low pH oxidative agent solution which includes Aculyn 22.RTM. which is insoluble in the oxidative agent solution, but dissolves to form a gel when mixed with alkaline dye lotion.
Hydrophobically modified cationic thickeners like Quatrisoft Polymer LM 200, an alkyl modified hydroxyethyl cellulose quaternary from Union Carbide Chemicals and Plastics Co. Inc., are commercially available. Due to their cationic nature these materials are not compatible with the anionic colored polymers described in this invention.
We have found that whereas many polymeric thickeners significantly reduce the resistance to redispersion in room temperature water of the colored polymers described in this invention, surprisingly, nonionic hydrophobically modified associative thickeners either by themselves or in combination with some surfactants can be conveniently used to increase product viscosity without compromising the bleed resistance and other important performance properties of such polymers when used in the temporary coloring of hair. We find that whereas the use of hydrophobically modified thickeners has been amply described in the patent literature, we find no prior art which anticipates the unique and unexpected properties of compositions comprising the colored polymer described in this invention, particularly in combination with nonionic hydrophobically modified associative thickeners.